Fabric treatment compositions

ABSTRACT

Fabric treatment compositions comprising a textile compatible carrier and particles having a layered structure comprising oxygen atoms and silicon and/or phosphorus atoms and comprising organic functional groups which are bonded to silicon and/or phosphorus atoms by direct covalent bonds between the silicon and/or phosphorus atoms and a carbon atom.  
     The functional groups are selected to impart lubricating properties to the particles.

TECHNICAL FIELD

[0001] This invention relates to fabric treatment compositions, to theiruse in the treatment of fabric and to a method of treating fabric withthe compositions.

BACKGROUND AND PRIOR ART

[0002] It is known that the physical properties of fabrics can bemodified by certain treatments. For example, fabric may be treated inorder to modify its physical properties either in an industrialpretreatment or during laundering.

[0003] Fabrics in general, and cotton in particular, are prone to theformation of creases before, during and after laundering and drying. Inorder to remove such creases from the fabric, a considerable amount oftime and effort must be spent ironing upon each occasion of launderingand drying. The terms “crease” and “wrinkle” and related terms, such as“anti-crease” and “anti-wrinkle”, refer to non-permanent deformations inthe fabric which can be removed by flattening at elevated temperatureand moisture (eg, by ironing) and are used synonymously herein.

[0004] Some of the previous attempts to address the problems of creaseformation with regard to fabrics have been based on the use of insolubleparticulate materials.

[0005] U.S. Pat. No. 3,892,681, for example, discloses the use ofgranular, substantially water-insoluble starch particles having adiameter between 1 to 45 μm in detergent compositions. Such particlesare said to impart anti-wrinkling and ease of ironing benefits inaddition to other fabric conditioning properties.

[0006] A detergent composition featuring a substantially water-insoluble particulate material with a diameter from about 5 to 30 μm isdescribed in U.S. Pat. No. 4,051,046. The particulate material may be aglass, ceramic or polymer-based bead, or a starch that has been treatedwith a hydrophobic agent to reduce its water solubility. In order topermit ironing, the particles must have a melting point above 150° C.These compositions are said to confer a range of fabric benefits,including anti-wrinkling and ease of ironing.

[0007] The use of smectite clay as a softening agent is disclosed inU.S. Pat. No. 3,936,537. In this document, the clay is combined with aquaternary ammonium salt, which confers anti-static benefits, and adispersion inhibitor consisting of a solid organic material, in adetergent compatible composition.

[0008] Smectite clay is also used in the fabric-softening detergentcompositions disclosed in U.S. Pat. No. 4,062,647. Again the clay issaid to impart improved softening and/or antistatic characteristics.

[0009] A fabric softening detergent composition comprising a syntheticnon-soap detergent, builder salt and clay is disclosed in GB 1400898.The clay, added for softening benefits, is a three-layer smectite-typeclay with an ion exchange capacity of at least 50 meq/100 g. Thecombination of builder salt and clay is described as helping preventagglomeration of the clay, thus allowing efficient deposition of theclay on fabric. In GB 1428061, a similar fabric softening composition isdisclosed with a water-insoluble quaternary ammonium salt present as ananti-static agent. The smectite-type clay, responsible for impartingsoftness benefits, has a particle size below 50 microns and anion-exchange capacity of at least 50 meq/100 grams.

[0010] In U.S. Pat. No. 5,443,750, clay, which may be smectite clay, isused 10 in conjunction with an enzyme in a detergent composition toafford increased softening properties.

[0011] EP-A-0 381 487 describes the use of liquid detergent compositionsin which a clay (an aluminosilicate eg, smectite) is treated with abarrier material, selected from a siloxane, a polysiloxane, apolyacrylate, dialkyl citrate, alkoxylated dialkyl citrate, alkoxylatedglycerol mono- and di-stearates, and alkoxylated N-alkyl alkanolamides,prior to incorporation of the clay into the formulation

[0012] The treatment of a range of water insoluble materials, includingclay, with an organosilicon compound bearing a quaternary ammonium groupis taught in U.S. Pat. No. 4,557,854. The organosilicon groups aregrafted onto the surface of the clay particles and, therefore, will bebound to the silicon atoms in the layers of the clay by way of Si—Olinkages. The effect of the treatment is described as being to increasethe cleaning power of conventional organic surface-active agents.

[0013] The treatment of cotton fabrics with cross-linking agents, suchas butane-1,2,3,4-tetracarboxylic acid (BTCA), is known to impartanti-wrinkle properties. However, such treatments tend to make thefabric stiff and relatively easy to tear.

[0014] U.S. Pat. No. 4,844,821 discloses liquid laundry detergent andliquid fabric softener compositions containing a smectite-type clayfabric softener in combination with an antisettling agent and,optionally, a softness enhancing amount of a polymeric clay-flocculatingagent.

[0015] U.S. Pat. No. 3,948,790 discloses detergent compositionscontaining a quaternary ammonium clay. The clay is an impalpablesmectite clay in which from 5 to 100 molar percent of the exchangeablecations are alkyl-substituted ammonium ions.

[0016] U.S. Pat. No. 4,828,723 discloses non-aqueous heavy duty laundrydetergent composition in the form of a suspension of a builder salt inliquid nonionic surfactant which is stabilised against phase separationby the addition of a low density filler and a small amount oforganophilic modified clay such as a water- swellable smectite clay inwhich the metal cations are fully or partially exchanged with mono- ordi-long chain quaternary ammonium compounds.

[0017] U.S. Pat. No. 5,336,647 discloses organophilic clay complexeswhich are dispersible in non-aqueous fluids to form a gel therein. Theorganophilic clay complex comprises the reaction product of

[0018] (a) a smectite-type clay;

[0019] (b) a first organic cation an amount of from about 75% to about150% of the cation exchange capacity of the smectite-type clay; and

[0020] (c) a second organic cation provided by a polyalkoxylatedquaternary ammonium salt; wherein the second organic cation is presentin an amount of from about 0.01% to about 20% by weight of the totalorganic cation content.

[0021] U.S. Pat. No. 5,527,871 discloses a layered inorganic-organicpolymer which has its inorganic portion in the form of a layeredclay-like structure composed of one or two sheets of tetrahedrons (whosecentral atom is Si or a metal) and a sheet of octahedrons (whose centralatom is a metal). The central atoms of the tetrahedrons are partially orentirely bonded to organic groups. The organic groups may containfunctional groups e.g. the functional groups may participate in apolymerisation reaction.

[0022] U.S. Pat. No. 4,287,086 discloses organophilic organic-claycomplexes which are dispersible in organic liquids to form a gel. Thegels may be useful as lubricating greases, oil base muds, oil basepacker fluids, paint-varnish-lacquer removers, paints and foundrymoulding sand binders. The organophilic clay is the reaction product ofa smectite clay and a methyl benzyl dialkyl ammonium salt.

[0023] U.S. Pat. No. 542,999 discloses an organophilic clay gellantuseful in a non-aqueous fluid system such as paints, inks and coatings.The organophilic clay gellant comprises the reaction product of:

[0024] (a) a smectite clay having a cation exchange capacity of at least75 milliequivalents per 100 grams of natural clay without impurities;

[0025] (b) a first organic cation in an amount of from about 75% toabout 150% of the cation exchange capacity of the smectite clay;

[0026] (c) a second organic cation provided by a polyalkoxylatedquaternary ammonium salt: and

[0027] (d) one or more organic anions(s) that is capable of reactingwith said first and second organic cations, to form an organiccation-organic anion complex with said smectite clay.

[0028] Co-pending PCT/EP01/12580 discloses fabric treatment compositioncomprising a textile compatible carrier and water insoluble particleshaving a layered structure comprising oxygen atoms and silicon and/orphosphorus atoms, and comprising organic functional groups which arebonded to silicon and/or phosphorus atoms in the layers by directcovalent bonds between the silicon and/or phosphorus atoms and a carbonatom.

[0029] In a preferred embodiment the use of fabric compositionscomprising water-insoluble particles having a layered structure andcomprising one or more organic functional groups which are capable ofself cross-linking and/or reacting with the fibres of the fabric leadsto improved anti-wrinkle, ie, crease reduction, performance of fabrics,without the disadvantages of conventional cross-linking agents such asbutane-1,2,3,4-tetracarboxylic acid (BTCA). Hence, fabrics treated withcompositions comprising such water-insoluble particles have goodantiwrinkle properties but are less stiff, less prone to discolouringand less susceptible to tearing than fabrics treated with someconventional cross-linking agents.

[0030] Cellulosic fibres possess hydroxyl groups; proteins possess arange of functional groups. Preferably, the organic functional groupscomprise electrophilic groups which are capable of reacting withhydroxyl groups for reaction with, for example, cellulosic fibres orproteinaceous fibres and/or thiol groups for more specific reaction, forexample, with proteinaceous fibres. Suitable examples of electrophilicgroups include: acid anhydrides, epoxides, acid chlorides, isocyanates,azetidinium-containing groups, carboxylic acids, vinyl sulfones,aldehydes, ketones, enol esters, aziridines, azalactones and mixturesthereof. The epoxide group is especially preferred.

[0031] It has now been found that a particular range of functionalgroups will provide particles capable of delivering enhanced lubricatingproperties to a fabric compared to particles without the functionalgroups.

[0032] According to one aspect of the present invention there isprovided fabric treatment composition comprising a textile compatiblecarrier and particles having a layered structure comprising oxygen atomsand silicon and/or phosphorus atoms, and comprising organic functionalgroups which are bonded to silicon and/or phosphorus atoms in the layersby direct covalent bonds between the silicon and/or phosphorus atoms anda carbon atom,

[0033] characterised in that the functional groups are selected from:

[0034] (i) a group of the formula:

—Y-T  (I)

[0035] in which;

[0036] Y comprises a chain of at least 6 carbon atoms optionallyinterrupted by one or more heteroatoms selected from N, O and Sproviding there are at least 3, preferably at least 4 carbon atoms foreach heteroatom in the chain, Y being linked to said silicon orphosphorous atom through a carbon atom, and

[0037] T represents H or a terminal groups which is not capable ofself-cross-linking and/or forming covalent bonds to cellulosic and/orproteinaceous fibres during domestic washing and rinsing cycles;

[0038] (ii) a group of the formula:

—R¹—NR²R²  (II)

[0039] in which:

[0040] R¹ represents an alkylene group of at least 4 carbon atoms,

[0041] each R² is independently lower alkyl and —NR²R² is preferably,but need not be, a terminal group;

[0042] (iii) a group of the formula: $\begin{matrix}\overset{+}{{—R}^{3}{—NR}^{4}R^{4}R^{4}} & ({III})\end{matrix}$

[0043] in which:

[0044] R³ represents an alkylene group of at least 3 carbon atoms,

[0045] each R⁴ is independently selected from alkyl groups of from 1 to25 carbon atoms provided at least one 4 is lower alkyl of 1 to 16 carbonatoms,

[0046] (iv) a group of the formula

[0047] in which each R_(1a) group is independently selected from C₁₋₄alkyl or hydroxyalkyl groups or C₂₋₄ alkenyl groups;

[0048] each R_(2a) group is independently selected from C₈₋₂₈ alkyl oralkenyl groups;

[0049] R_(3a) is a linear or branched alkylene group of 1 to 5 carbonatoms,

[0050] X is

[0051] and p is 0 or is an integer from 1 to 5,

[0052] with the proviso that one of R_(1a) and R_(2a) is an alkylenegroup of at least 3 carbon atoms attached to said silicon or phosphorusatom;

[0053] (v) a group of the formula:

[0054] in which R_(1a), p and R_(2a) are as defined above;

[0055] (vi) a group of the formula:

[0056] in which:

[0057] T is as defined above,

[0058] R⁵ represents a group of at least one carbon atom, preferably atleast 3 carbon atoms, which may be interrupted by one or moreheteroatoms selected from N, O and S providing there are at least 3carbon atoms for each heteroatom,

[0059] n is an integer of at least 6; and

[0060] (vii) a group of the formula:

[0061] in which:

[0062] T and R⁵ are as defined above,

[0063] each R⁶ independently represents an alkyl group, a fluorinatedalkyl group, an amino substituted alkyl group, an alkyl groupsubstituted with a sugar moiety, or a sidechain comprising anethoxylated and/or propoxylated chain, and

[0064] x is an integer of at least 5.

[0065] The organic functional groups are selected to delivery enhancedlubricating properties compared to corresponding materials which do notpossess the functional groups. When applied to fabrics the materialsprovide a lubricating effect reducing the inter-yarn friction at theyarn/yarn contacts. The effect of the materials can be assessed byKawabata shear as discussed hereinafter. The enhanced lubricatingproperties may provide improved softness, ease of ironing, anti-wrinkle,anti-abrasion and related benefits.

[0066] The materials may be used to treat fabric by simply bringing themin contact with the fabric. The materials are water dispersible and maybe delivered to the fabric in the main wash or in the rinse conditioner.The lubrication performance delivered by these materials can exceed thelubrication performance delivered by conventional rinse conditionercationic surfactant systems.

[0067] The desired functional groups may be introduced during thesynthesis of the materials, through post-modification of pre-synthesisedfunctional materials or modification of an existing clay.

[0068] The present invention involves the use of particles having alayered structure comprising oxygen atoms and silicon and/or phosphorusatoms, and comprising organic functional groups which are bonded tosilicon and/or phosphorus atoms in the layers by direct covalent bondsbetween the silicon and/or phosphorus atoms and a carbon atom. Theparticles tend to be water-insoluble. The particles are dispersible inwater at 20° C. and in some cases will appear to give solutions as theymay break down into submicron fragments.

[0069] The particles used in the invention are of a size such that theyare not perceived as distinct particles to the touch. Preferably, theparticles used in the invention have an average size of from 0.01 to 100μm. More preferably, the particles used herein have an average size inthe range of from about 1 μm to 50 μm. The size of the particles refersto their maximum dimension, such as their diameter when the particlesare substantially spherical.

[0070] The layered nature of the particles preferably involves anordered array comprising oxygen atoms and silicon and/or phosphorusatoms. The layers may also comprise other metallic and/or non-metallicatoms. Other atoms which may be present in the layers include, forexample, di- and/or tri-valent metal atoms, such as of alkaline earthmetals (eg, magnesium or calcium), of transition metals (eg, copper,nickel and/or zirconium), of Group IIIB of the periodic table (eg,aluminum) or of mixtures thereof. Suitable particles may comprisediscrete, repeating units of layers or sheets. Layers or sheets aresubstantially two- dimensional arrays of atoms. Preferably, therepeating unit consists of a plurality of (eg, two or three) layers, orsheets, of atoms with a metallic atom or a mixture of metallic atomsforming the central layer and a range of non- metallic atoms bridgingand/or forming the surrounding layers. Also present within the repeatingunit may be a variety of atomic, ionic or molecular species, includingfor example, polyvalent metal ions such as sodium and/or calcium and/orhydroxonium ions.

[0071] Suitable examples of layered structures include those comprisingdivalent or trivalent metal ions, or a mixture thereof, in the centrallayer. Preferably, the central layer comprises magnesium, nickel oraluminium ions, or mixtures thereof, which are connected via oxygenatoms and/or hydroxyl groups to the surrounding layer. Preferably, thesurrounding layers comprise a mixture of silicon atoms and oxygen atomsas well as other cationic and/or molecular species.

[0072] The interlayer spacing in the particles which are used in theinvention is preferably greater than 10×, more preferably greater than12×, as determined by X-ray crystallography. The interlayer spacingpreferably does not exceed about 100× and, more preferably, it does notexceed about 50×.

[0073] When the central layer comprises divalent ions and the outerlayer comprises silicon atoms, with bridging oxygen atoms and hydroxylgroups, the layered structure is analogous to that of talc-likesmectite, or phyllosilicate clays.

[0074] Smectite clays can broadly be differentiated on the basis of thenumber of octahedral metal-oxygen arrangements in the central layer fora given number of silicon-oxygen atoms in the outer layer. Those claysfeaturing primarily divalent metal ions comprise the prototype talc andthe members hectorite, saponite, sauconite and vermiculite. When theclays feature primarily trivalent metal ions the structures change andnow comprise the prototype pyrophillite, montmorillonite, nontronite andvolchonskoite.

[0075] The particles comprise one or more organic functional groups. Thefunctional groups in each particle may be a single type of functionalgroup or a mixture of different types of functional groups. Theseorganic functional groups can be at least partly responsible forconferring the desired properties on the fabric, after treatment withthe particles or compositions comprising the particles.

[0076] The functional groups of formula (I) are preferably long chainalkyl or alkylene groups preferably having at least 6, or preferablyfrom 8 to 20 carbon atoms. Alkyl groups are preferred.

[0077] The terminal group T may be hydrogen or any group which is notcapable of self-cross-linking and/or forming covalent bonds to celluloseand/or proteinaceous fibres during domestic washing and rinsing cycles.For enhanced lubrication, there should be no stiffening of the fabric bythe materials crosslinking or bonding to the fibres. In general, if aterminal group is present, it is selected to improve the dispersibilityof the material. Suitable groups include alkyl, ether, carboxylic acid,sulphonate, sulphate, phosphate and phosphinate groups.

[0078] In the groups of formula (II), the amine group is linked via R¹which is an alkylene group of at least 4 carbon atoms. At least 1,preferably both, of the R² groups is an alkyl group of at least 8 carbonatoms.

[0079] The quaternary group of formula (III) is linked via R³ whichrepresents an alkylene group of at least 3 carbon atoms. R³ may have along chain e.g. up to 20 carbon atoms.

[0080] Generally, 1 or 2 of the R⁴ groups is lower alkyl e.g. methyl andthe other has a longer chain length e.g. up to 20 carbon atoms. In oneembodiment, two of the R⁴ groups are long chain alkyl groups.

[0081] The groups of formula (IV) and (V) are based upon the structureof known cationic fabric softening compounds. It is possible tointroduce these groups into the material of the particles either duringsynthesis of the material or through post-modification of apre-synthesised functional clay.

[0082] Similarly, it is possible to introduce a polyethylene glycolchain as a functional group as represented by formula (VI) and asilicone chain as represented by formula (VII). The silicone backbonemay have side chains in a similar manner to known silicone polymers.Suitable side chains include alkyl groups, perfluro side chains, sidechains having amino functionality, side chains having sugar moieties andepoxylated and/or propoxylated side chains.

[0083] The materials may comprise a mixture of two or more functionalgroups.

[0084] Materials having octyl and dodecyl groups are disclosed inUkrainczyk, R. A. Bellman, A. B. Anderson, J. Phys. Chem. B., 1997, 101,531-539.

[0085] Compounds having the functional groups of formula (II) to (VII)are believed to be new and form a further aspect of the invention.

[0086] The particles are preferably of a clay functionalised by theintroduction-of organic functional groups during its synthesis. Theorganic functional groups may be converted to different organicfunctional groups by reaction of the clay, after it has beensynthesised, with an appropriate reagent, to form another clay which issuitable for use in the present invention. Appropriate reagents andreaction conditions for the interconversion of functional groups arewell-known to those skilled in the art. Alternatively, the clay may needno conversion of functional groups prior to use in the compositions ofthe invention.

[0087] More preferably, the functionalised particles are of the generalclass of inorganic-organic hybrid clays known as anorgano(phyllosilicates). Examples of synthetic methods for formingorgano(phyllosilicates), or organoclays, are described in J. Mater.Chem., vol. 8, 1998, p 1927-1932, J. Phys. Chem. B. 1997, 101, 531-539,J. Chem. Soc., Chem. Commun., 1995, 241-242 and J. Mater. Chem. 2000,10, 1457-1463. In these examples, the organic functionality isintroduced into the clay by assembling a metal oxide/hydroxide frameworkin the presence of an organotrialkoxysilane. The particles of thepresent invention are preferably produced according to this method.Therefore, the particles are preferably obtainable by the hydrolysis ofan organotrialkoxysilane in the presence of at least one di- ortri-valent metal ion in an alcoholic solution at a suitable pHappropriate to the metal ion used. The skilled person is readily able todetermine a suitable pH for the hydrolysis on the basis of the teachingof the prior art. For example, for magnesium, the pH is typicallygreater than 7 and for aluminium it will typically be in the range offrom pH 5-12 (preferably from 5.5 to 6.5).

[0088] Other functionalised particles are also suitable for use in thepresent invention. For example, metal organophosphates (includingzirconium (which is preferred), titanium, hafnium, vanadium (V),magnesium (II), manganese (II), calcium (II), cadmium (II), lanthanum(III), samarium (III), cerium (III) and iron (III)) can be prepared by aprecipitation reaction involving mixing a solution of the metal ion anda solution of an organic phosphoric or phosphinic acid. Crystallisationof the layered structure results. Synthetic routes of this type aredescribed, for example, in Acc. Chem. Res., 1992, 25, 420-427, Chem.Mater. 1994, 6, 2227, Acc. Chem. Res., 1978, 11, 163 and Chem. Rev.,1988, 88, 55. Zirconium organophosphates, and other metalorganophosphates, typically comprise, in each layer, a plane of metalatoms linked together by phosphonate groups. The metal atoms arepreferably octahedrally coordinated by oxygen atoms, with the threeoxygen atoms of each phosphonate tetrahedron bound to three differentmetal atoms.

[0089] The preferred particles used in the invention are organoclays andmore preferably three-layer clays consisting of a centralmetal-containing layer, as in the analogous talc-like structures,together with bridging oxygen and hydroxyl groups and silicon atoms inthe outer two layers. Unlike talc, however, the outer silicon atoms areattached to organic groups as well as oxygen atoms. Preferably, a highproportion (for example greater than 50% by number, more preferablygreater than 75% by number) of the Si atoms in any given organoclayparticle are covalently bonded to at least one carbon atom. However, thelayered structure may contain varying amounts of Si atoms that are notcovalently bonded to a carbon atom, and these particles will alsooperate effectively within the scope of the invention.

[0090] The organoclays preferably comprise silicon or phosphorus,oxygen, metal (eg, magnesium, nickel, zirconium or aluminium or mixturesthereof) and, optionally, hydrogen atoms, in addition to the organicfunctional groups and the organic functional groups in the waterinsoluble particles.

[0091] Preferred particles of the invention may have the general formula(without the functional groups)

M_(x)Si_(8−y)O_(16−3y)(OH)_(4+3y),

[0092] wherein:

[0093] M is Mg, Ni, Cu or Al

[0094] x is 6 when M is Mg, Ni or Cu; and 4 when M is Al

[0095] y is between 0 and 4

[0096] In a particularly preferred example of the invention, theorganoclay may be represented by the formula Mg₆Si₈R₈O₁₆(OH)₄, with asilicon to magnesium ratio of 1.33 and where R is any one of thesuitable organic functional groups listed above. Again, the particlesare conveniently functionalised by virtue of a direct Si—C covalent bondcreated during the synthesis of the whole material, not by syntheticpost- modification (eg, by grafting onto the surface of a preformed clayparticle); this allows far more organic functional groups to beIncorporated at the surface of, and/or within the layers of, theparticle.

[0097] Treatment of fabric with the fabric treatment compositions of theinvention comprises any step in which the compositions are applied tofabric.

[0098] Typically, application occurs with the composition in the form ofan aqueous dispersion or suspension. Treatments include laundering ofthe fabric.

[0099] The fabric preferably comprises synthetic or non-synthetic fibresor mixtures thereof. Non-synthetic fibres include, for example,cellulosic (eg, cotton) or proteinaceous (eg, wool or silk) fibres.Synthetic fibres include, for example, nylons and polyesters.

[0100] The invention may also be carried out in non-domesticenvironments. For example, the method of the invention may involve thetreatment of fabric (before or after it has been made into finishedarticles such as garments) on an industrial scale.

[0101] The particles having a layered structure and comprising one ormore organic functional groups are preferably present in the fabrictreatment composition in an amount of from 0.01% to 50% by weight of thecomposition; more preferably they are present in an amount of from 0.1%to 20% by weight of the composition, most preferably 0.1-10% by weightof the composition. However, the particles may be supplied asconcentrates e.g. for adding to a treatment liquor, in which case theparticles may be present in concentrations up to 100%.

[0102] The fabric treatment composition contains one or more textilecompatible carriers.

[0103] The nature of the textile compatible carrier will be dictated toa large extent by the stage at which the composition of the invention isused in a laundering process, the compositions being capable of beingused, in principle, at any stage of the process. For example, where thecompositions are for use as main wash detergent compositions, which ispreferred, the one or more textile compatible carriers comprise adetergent active compound. Where the compositions are for use in therinsing step of a laundering process, the one or more textile compatiblecarriers may comprise a fabric softening and/or conditioning compound.

[0104] The compositions of the invention preferably comprise a perfume,such as of the type which is conventionally used in fabric carecompositions. The compositions may be in the form of packaged articleswhich are labelled as being for use in a domestic laundering process.

[0105] The textile compatible carrier is a component which can assist inthe interaction of the first component with the fabric. The carrier canalso provide benefits in addition to those provided by the firstcomponent e.g. softening, cleaning etc.

[0106] If the composition of the invention is to be used before, orafter, the laundry process it may be in the form of a spray or foamingproduct.

[0107] The laundering processes of the present invention include thelarge scale and small scale (eg domestic) cleaning of fabrics. Suitablefabrics include fabrics which are in the form of garments. Preferably,the processes are domestic

[0108] Detergent Active Compounds

[0109] If the composition of the present invention is in the form of adetergent composition, the textile-compatible carrier may be chosen fromsoap and non-soap anionic, cationic, nonionic, amphoteric andzwitterionic detergent active compounds, and mixtures thereof.

[0110] Many suitable detergent active compounds are available and arefully described in the literature, for example, in “Surface-ActiveAgents and Detergents”, Volumes I and II, by Schwartz, Perry and Berch.

[0111] The preferred textile-compatible carriers that can be used aresoaps and synthetic non-soap anionic and nonionic compounds.

[0112] Anionic surfactants are well-known to those skilled in the art.Examples include alkylbenzene sulphonates, particularly linearalkylbenzene sulphonates having an alkyl chain length of C₈-C₁₅; primaryand secondary alkylsulphates, particularly C₈-C₁₅ primary alkylsulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylenesulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.Sodium salts are generally preferred.

[0113] Nonionic surfactants that may be used include the primary andsecondary alcohol ethoxylates, especially the C₈-C₂₀ aliphatic alcoholsethoxylated with an average of from 1 to 20 moles of ethylene oxide permole of alcohol, and more especially the C₁₀-C₁₅ primary and secondaryaliphatic alcohols ethoxylated with an average of from 1 to 10 moles ofethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactantsinclude alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides(glucamide).

[0114] Cationic surfactants that may be used include quaternary ammoniumsalts of the general formula R₁R₂R₃R₄N⁺X⁻ wherein the R groups areindependently hydrocarbyl chains of C₁-C₂₂ length, typically alkyl,hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation(for example, compounds in which R₁ is a C₈-C₂₂ alkyl group, preferablya C₈-C₁₀ or C₁₂-C₁₄ alkyl group, R₂ is a methyl group, and R₃ and R₄,which may be the same or different, are methyl or hydroxyethyl groups);and cationic esters (for example, choline esters) and pyridinium salts.

[0115] The total quantity of detergent surfactant in the composition issuitably from 0.1 to 60 wt % e.g. 0.5-55 wt %, such as 5-50 wt %.

[0116] Preferably, the quantity of anionic surfactant (when present) isin the range of from 1 to 50% by weight of the total composition. Morepreferably, the quantity of anionic surfactant is in the range of from 3to 35% by weight, e.g. 5 to 30% by weight.

[0117] Preferably, the quantity of nonionic surfactant when present isin the range of from 2 to 25% by weight, more preferably from 5 to 20%by weight.

[0118] Amphoteric surfactants may also be used, for example amine oxidesor betaines.

[0119] The compositions may suitably contain from 10 to 70%, preferablyfrom 15 to 70% by weight, of detergency builder. Preferably, thequantity of builder is in the range of from 15 to 50% by weight.

[0120] The detergent composition may contain as builder a crystallinealuminosilicate, preferably an alkali metal aluminosilicate, morepreferably a sodium aluminosilicate.

[0121] The aluminosilicate may generally be incorporated in amounts offrom 10 to 70% by weight (anhydrous basis), preferably from 25 to 50%.Aluminosilicates are materials having the general formula:

0.8-1.5M₂O.Al₂O₃.0.8-6SiO₂

[0122] where M is a monovalent cation, preferably sodium. Thesematerials contain some bound water and are required to have a calciumion exchange capacity of at least 50 mg CaO/g. The preferred sodiumaluminosilicates contain 1.5-3.5 SiO₂ units in the formula above. Theycan be prepared readily by reaction between sodium silicate and sodiumaluminate, as amply described in the literature.

[0123] Fabric Softening and/or Conditioner Compounds

[0124] If the composition of the present invention is in the form of afabric conditioner composition, the textile-compatible carrier will be afabric softening and/or conditioning compound (hereinafter referred toas “fabric softening compound”), which may be a cationic or nonioniccompound.

[0125] The softening and/or conditioning compounds may be waterinsoluble quaternary ammonium compounds. The compounds may be present inamounts of up to 8% by weight (based on the total amount of thecomposition) in which case the compositions are considered dilute, or atlevels from 8% to about 50% by weight, in which case the compositionsare considered concentrates.

[0126] Compositions suitable for delivery during the rinse cycle mayalso be delivered to the fabric in the tumble dryer if used in asuitable form. Thus, another product form is a composition (for example,a paste) suitable for coating onto, and delivery from, a substrate e.g.a flexible sheet or sponge or a suitable dispenser during a tumble dryercycle.

[0127] Suitable cationic fabric softening compounds are substantiallywater-insoluble quaternary ammonium materials comprising a single alkylor alkenyl long chain having an average chain length greater than orequal to C₂₀ or, more preferably, compounds comprising a polar headgroup and two alkyl or alkenyl chains having an average chain lengthgreater than or equal to C₁₄. Preferably the fabric softening compoundshave two long chain alkyl or alkenyl chains each having an average chainlength greater than or equal to C₁₆. Most preferably at least 50% of thelong chain alkyl or alkenyl groups have a chain length of C₁₈ or above.It is preferred if the long chain alkyl or alkenyl groups of the fabricsoftening compound are predominantly linear.

[0128] Quaternary ammonium compounds having two long-chain aliphaticgroups, for example, distearyldimethyl ammonium chloride and di(hardenedtallow alkyl) dimethyl ammonium chloride, are widely used incommercially available rinse conditioner compositions. Other examples ofthese cationic compounds are to be found in “Surface-Active Agents andDetergents”, Volumes I and II, by Schwartz, Perry and Berch. Any of theconventional types of such compounds may be used in the compositions ofthe present invention.

[0129] The fabric softening compounds are preferably compounds thatprovide excellent softening, and are characterised by a chain melting Lβto Lα transition temperature greater than 25° C., preferably greaterthan 35° C., most preferably greater than 45° C. This Lβ to Lαtransition can be measured by DSC as defined in “Handbook of LipidBilayers”, D Marsh, CRC Press, Boca Raton, Fla., 1990 (pages 137 and337).

[0130] Substantially water-insoluble fabric softening compounds aredefined as fabric softening compounds having a solubility of 25 lessthan 1×10⁻³ wt % in demineralised water at 20° C. Preferably the fabricsoftening compounds have a solubility of less than 1×10⁻⁴ wt %, morepreferably less than 1×10⁻⁸ to 1×10⁻⁶ wt %.

[0131] Especially preferred are cationic fabric softening compounds thatare water-insoluble quaternary ammonium materials having two C₁₂₋₂₂alkyl or alkenyl groups connected to the molecule via at least one esterlink, preferably two ester links. An especially preferred ester-linkedquaternary ammonium material can be represented by the formula (VIII):

[0132] wherein each R_(1a) group is independently selected from C₁₋₄alkyl or hydroxyalkyl groups or C₂₋₄ alkenyl groups; each R_(2a) groupis independently selected from C₈₋₂₈ alkyl or alkenyl groups; andwherein R_(3a) is a linear or branched alkylene group of 1 to 5 carbonatoms, X is

[0133] and p is 0 or is an integer from 1 to 5.

[0134] Di(tallowoxyloxyethyl) dimethyl ammonium chloride and/or itshardened tallow analogue is especially preferred of the compounds offormula (VIII).

[0135] A second preferred type of quaternary ammonium material can berepresented by the formula (IX):

[0136] wherein R_(1a), p and R_(2a) are as defined above.

[0137] It is advantageous if the quaternary ammonium material isbiologically biodegradable.

[0138] Preferred materials of this class such as 1,2-bis(hardenedtallowoyloxy)-3-trimethylammonium propane chloride and their methods ofpreparation are, for example, described in U.S. Pat. No. 4,137,180(Lever Brothers Co). Preferably these materials comprise small amountsof the corresponding monoester as described in U.S. Pat. No. 4,137,180,for example, 1-hardened tallowoyloxy-2-hydroxy-3-trimethylammoniumpropane chloride.

[0139] Other useful cationic softening agents are alkyl pyridinium saltsand substituted imidazoline species. Also useful are primary, secondaryand tertiary amines and the condensation products of fatty acids withalkylpolyamines.

[0140] The compositions may alternatively or additionally containwater-soluble cationic fabric softeners, as described in GB 2 039 556B(Unilever).

[0141] The compositions may alternatively or additionally contain thepolyol polyester (eg, sucrose polyester) compounds described in WO98/16538.

[0142] The compositions may comprise a cationic fabric softeningcompound and an oil, for example as disclosed in EP-A-0829531.

[0143] The compositions may alternatively or additionally containnonionic fabric softening agents such as lanolin and derivativesthereof.

[0144] Lecithins are also suitable softening compounds.

[0145] Nonionic softeners include Lβ phase forming sugar esters (asdescribed in M Hato et al Langmuir 12, 1659, 1666, (1996)) and relatedmaterials such as glycerol monostearate or sorbitan esters. Often thesematerials are used in conjunction with cationic materials to assistdeposition (see, for example, GB 2 202 244). Silicones are used in asimilar way as a co-softener with a cationic softener in rinsetreatments (see, for example, GB 1 549 180).

[0146] The compositions may also suitably contain a nonionic stabilisingagent. Suitable nonionic stabilising agents are linear C₈ to C₂₋₂alcohols alkoxylated with 10 to 20 moles of alkylene oxide, C10 to C₂₀alcohols, or mixtures thereof.

[0147] Advantageously the nonionic stabilising agent is a linear C₈ toC₂₋₂ alcohol alkoxylated with 10 to 20 moles of alkylene oxide.Preferably, the level of nonionic stabiliser is within the range from0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, mostpreferably from 1 to 4% by weight. The mole ratio of the quaternaryammonium compound and/or other cationic softening agent to the nonionicstabilising agent is suitably within the range from 40:1 to about 1:1,preferably within the range from 18:1 to about 3:1.

[0148] The composition can also contain fatty acids, for example C₈ toC₂₄ alkyl or alkenyl monocarboxylic acids or polymers thereof.Preferably saturated fatty acids are used, in particular, hardenedtallow C₁₆ to C₁₈ fatty acids.

[0149] Preferably the fatty acid is non-saponified, more preferably thefatty acid is free, for example oleic acid, lauric acid or tallow fattyacid. The level of fatty acid material is preferably more than 0.1% byweight, more preferably more than 0.2% by weight. Concentratedcompositions may comprise from 0.5 to 20% by weight of fatty acid, morepreferably 1% to 10% by weight. The weight ratio of quaternary ammoniummaterial or other cationic softening agent to fatty acid material ispreferably from 10:1 to 1:10.

[0150] The fabric conditioning compositions may include silicones, suchas predominately linear polydialkylsiloxanes, e g. polydimethylsiloxanesor aminosilicones containing amine-functionalised side chains; soilrelease polymers such as block copolymers of polyethylene oxide andterephthalate; amphoteric surfactants; smectite type inorganic clays;zwitterionic quaternary ammonium compounds; and nonionic surfactants.

[0151] The fabric conditioning compositions may be in the form ofemulsions or emulsion precursors thereof.

[0152] Other optional ingredients include emulsifiers, electrolytes (forexample, sodium chloride or calcium chloride) preferably in the rangefrom 0.01 to 5% by weight, pH buffering agents, and perfumes (preferablyfrom 0.1 to 5% by weight).

[0153] Further Optional Ingredients

[0154] Further optional ingredients in the compositions of the inventioninclude non-aqueous solvents, perfume carriers, fluorescers, colourants,hydrotropes, antifoaming agents, antiredeposition agents, enzymes,optical brightening agents, opacifiers, dye transfer inhibitors,anti-shrinking agents, anti-wrinkle agents, anti-spotting agents,germicides, fungicides, anti-oxidants, UV absorbers (sunscreens), heavymetal sequestrants, chlorine scavengers, dye fixatives, anti-corrosionagents, drape imparting agents, antistatic agents, ironing aids, bleachsystems, soil release agents and unmodified smectite clays. This list isnot intended to be exhaustive.

[0155] The compositions of the invention may also include an agent whichproduces a pearlescent appearance, e.g. an organic pearlising compoundsuch as ethylene glycol distearate, or inorganic pearlising pigmentssuch as microfine mica or titanium dioxide (TiO₂) coated mica.

[0156] An anti-settling agent may be included in the compositions of theinvention. The anti-settling agent, which reduces the tendency of solidparticles to separate out from the remainder of a liquid composition, ispreferably used in an amount of from 0.5 to 5% by weight of thecomposition. Organophilic quaternised ammonium-clay compounds and fumedsilicas are examples of suitable anti-settling agents.

[0157] A further optional ingredient in the compositions of theinvention is a flocculating agent which may act as a delivery aid toenhance deposition of the active ingredients (such as the waterinsoluble particles) onto fabric. Flocculating agents may be present inthe compositions of the invention in amounts of up to 10% by weight,based on the weight of the organoclay. Suitable flocculating agentsinclude polymers, for example long chain polymers and copolymerscomprising repeating units derived from monomers such as ethylene oxide,acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinylalcohol, vinyl pyrrolidone, ethylene imine and mixtures thereof. Gumssuch as guar gum, optionally modified, are also suitable for use asflocculating agents.

[0158] Other possible delivery aids for the particles include, forexample, the water-soluble or water-dispersible rebuild agents (eg,cellulose monoacetate) described in WO 00/18860.

[0159] Fabric Treatment Products

[0160] The composition of the invention may be in the form of a liquid,solid (e.g. powder or tablet), a gel or paste, spray, stick or a foam ormousse. Examples including a soaking product, a rinse treatment (e.g.conditioner or finisher) or a mainwash product. The composition may alsobe applied to a substrate e.g. a flexible sheet or used in a dispenserwhich can be used in the wash cycle, rinse cycle or during the dryercycle.

[0161] The compositions may include adjunct components imparting otherbeneficial properties to the products e.g. lubricants, such assilicones, anti-wrinkling agents, such as lithium salts, and perfumeingredients, such as cyclodextrins and fragrances.

[0162] The invention will now be described by way of example only andwith reference to the following non-limiting examples. In the examplesand throughout this specification all percentages are percentages byweight unless indicated otherwise.

[0163] In the following Examples assessment of fabric softeners and thelubrication effect of the clay additives was assessed by Kawabata shearas disclosed, for example, in Melliard Testilbericht 67 (1986) pp509-516. Samples were tested using a Kawabata KES-FBI machine, Kato TechCorporation Ltd. Japan. In this machine samples are laced between twoclamps which are movable relative to each other.

[0164] For each test, six replicas (20 cm square) were used.

[0165] After treatment(s) samples were dried and ironed flat.

[0166] Samples left to condition for 24 hours prior to testing. Alltesting was conducted in a test room at 65% r.h. and 20° C.

[0167] The specimen is subjected to cyclic shear deformation, themaximum displacement (shear angle) being 8°.

[0168] Shear stiffness is highly correlated with the tightness of fabricconstruction and the inter-yarn friction at yarn/yarn contacts. Shearhysteresis is directly related to the size of the frictional forcesoperating between yarns and is highly correlated with perceived softnessin some fabric constructions. From the shear hysteresis loop, thefollowing parameters are obtained.

[0169] G: fabric stiffness in shear. Slope of the hysteresis curvebetween 0.5° and 2.5° shear angle—an average of positive and negativeregions of the curve is taken.

[0170] 2HG: width of the hysteresis loop at 0.5° shear angle—average ofvalues measured at 0.5° and −0.5° is taken.

[0171] 2HG5: width of the hysteresis loop at 5° shear angle—average ofvalues measured at 50 and −5° is taken.

[0172] Comparative softeners/lubrication effect was assessed by shearhysteresis at 50 shear angle (2HG5). A decrease in shear hysteresisreflects increased softness/lubrication performance.

EXAMPLES 1-5

[0173] Standard Synthesis of Magnesium (organo) Phyllosilicates

[0174] Examples 1 to 5 employed a direct one-step approach, in whichproducts were precipitated from basic alcoholic solutions. Typically,magnesium chloride hexahydrate, MgCl₂.6H₂O was charged to a reactionvessel and ethanol/methanol was added. Stirring was employed to dissolvethe magnesium salt. Organotrialkoxysilane was added, under rapidstirring, followed immediately by the addition of sodium hydroxidesolution (0.05 M). The resultant reaction mixture was stirred at roomtemperature for a minimum of 1 hour. The product of the reaction wasisolated by filtration or centrifugation and washed with copious waterand ethanol. The products may be retained as a slurry in water, dried inair or with or without heating, dried under vacuum with or withoutheating or freeze-dried.

[0175] The amount of organotrialkoxysilane added in each case was equalto the stoichiometric amount required to synthesise materials withSi/Mg=1.33. Molar ratios of approx. Si:Mg:OH=1:0.75:0.90 were employedin the synthesis.

[0176] The following starting precursors were used in Examples 1 to 5:Example Organotrialkoxysilane Precursor 1 Octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride 2 Hexyltriethoxysilane 3Octyltriethoxysilane 4 Dodecyltriethoxysilane 5 (3-Glycidoxypropyl)trimethoxysilane

[0177] Example 5 is not a material for use in fabric treatment inaccordance with the invention but is an example of a clay having afunctional group which can be used in a reaction to introduce functionalgroups in accordance with the invention.

EXAMPLES 6 to 8

[0178] Alcoholic, Base-Free Synthesis of Magnesium Amino-Containing(Organo)Phyllosilicates

[0179] Examples 6 to 8 employed an alternative method for preparation ofamino-containing magnesium organoclays employed base-free, alcoholicconditions. Magnesium chloride hexahydrate, MgCl₂.6H₂O, was dissolved inethanol or methanol and organotrialkoxysilane was added with rapidstirring. Immediate clouding of the solution followed by copiousprecipitation ensued after 5 minutes stirring. The reaction mixture wasleft stirring at room temperature for a minimum of 1 hour. The productof reaction was isolated by filtration and washed thoroughly withethanol. The products of the reaction may be redispersed in ethanol orwater and retained as a slurry, dried in air with or without heating,dried under vacuum with or without heating or freeze-dried.

[0180] The amount of organotrialkoxysilane added in each case was equalto the stoichiometric amount required to synthesise materials withSi/Mg=1.33.

[0181] The following starting precursors were used in Examples 6 to 8:Example Organotrialkoxysilane Precursor 6 3-Aminobutyltriethoxysilane 74-Aminobutyltriethoxysilane 8 N-Trimethoxysilylpropyl-N, N, N-trimethylammonium chloride

EXAMPLES 9 to 16

[0182] The utility of the pendant epoxide group 3-glycidoxypropyl on theclay of Example 5 (epoxide clay) to post-functionalisation bynucleophiles was utilised to introduce alternative functional groups.

EXAMPLE 9

[0183] The epoxide group was initially ring-opened by heating with anexcess of ethylenediamine to give an amine-terminated clay. Aftercontinuous extraction with acetone the dried clay contained nitrogen byelemental analysis. The prepared amino clay was then reacted withsuccinic anhydride to give a clay with an acid functionality, the FTIRof the clay showed evidence of an amide and carboxylicacid carbonylstretch.

EXAMPLES 11 to 12

[0184] The functionalisation of the epoxide clay with amino- terminalpolyethyleneglycols (Jeffamines) was analogous to the reaction of theclay with ethylenediamine, whereby the clays were heated with an excesssolution of the oligomeric amines and exhaustively extracted afterfunctionalisation. The covalent attachment of the oligomers was shown bythe presence of nitrogen in the elemental analysis. In total threeJeffamine variants were reacted; two α, ω-diamines with molecularweights of 2,000 (Example 10) and 3,000 (Example 11) and a mono aminewith a molecular weight of 1,000 (Example 12).

EXAMPLES 13 to 16

[0185] Polydimethylsiloxane (PDMS)-functionalised clays were preparedvia the reaction of the epoxide clays with α, ω-diamino PDMS (900, 2000and 3,000 mwts) (Examples 13 to 15) and α, ω-dihydroxy PDMS oligomers.(Example 16). In the case of the diamine simply heating the epoxide claywith the diamine was sufficient to ring-open the epoxide while the diolrequired the use of 1 equivalent of sodium hydride to form the morenucleophilic alkoxide.

EXAMPLE 17

[0186] Synthesis of clay having the functional group —C₃(PEG)₆₋₉OCH₃.Magnesium chloride hexahydrate was charged to a reaction vessel andethanol or methanol was added. Stirring was employed to dissolve themagnesium salt. The organotrialkoxysilane,2-[method(polyethyleneoxy)propyl]trimethoxysilane, was added under rapidstirring, followed immediately by the addition of sodium hydroxidesolution (0.05M). The reaction mixture was stirred at room temperaturefor a minimum of one hour. Ethanol and methanol were removed from thereaction mixture by rotary evaporation and the resultant mixture wasfreeze- dried.

[0187] The amount of organtrialkoxysilane added in the experiment wasequal to the stoichiometric amount required to synthesise materials withSi/Mg=1.33. Molar ratios of approx. Si:Mg:OH=1:0.75:0.90 were employedin the synthesis.

EXAMPLE 18

[0188] Synthesis of a Mixed Functional Group Clay.

[0189] Magnesium chloride hexahydrate was charged to a reaction vesseland stirred to dissolution. Two organotrialkoxysilanes were added underrapid stirring, followed immediately by the addition of sodium hydroxidesolution (0.05M). The resultant reaction mixture was stirred at roomtemperature for a minimum of one hour. The product of the reaction wasisolated by filtration and washing with ethanol. The solid product wasdried at room temperature.

[0190] A 50:50 stoichiometric mix of 2-[methoxy (polyethyleneoxy)propyl]trimethoxysilane and octadecyldimethyl (3-trimethoxysilylpropyl)ammonium chloride was used in amounts equal to an overall Si/Mg=1.33Molar ratios of approx. Si:Mg:OH=1:0.75:0.90 were employed in thesynthesis.

EXAMPLE 19

[0191] Delivery of Functionalised Clay from a Liquid DetergentComposition

[0192] The following detergent composition was used: Anionic surfactants20% (Sodium benzylsulfonate + sodium alcohol EO sulfate) Nonionicsurfactant (Alkyl ethoxylate)  5% Sodium citrate  4%

[0193] Washing Procedure

[0194] The following wash conditions were employed: Product Fabricwashing liquid formulation (A) 1.69 g/litre Functionalised 0, 2.5, 5 and10% by weight of clay formulation (A) Fabric Two swatches of Oxfordcotton measuring 40 × 40 cm cut into 20 × 20 cm squares, total fabricweight 40 g, the warp direction was marked on each piece with anindelible pen. Liquor 950 ml of demineralised water and 50 ml ofdemineralised water containing the required level of functionalisedclay, overall liquor to cloth ratio 25:1 Apparatus Tergotometer set at75 rpm Wash time 15 minutes Wash temperature 35° C. After wash Fabricsremoved, squeezed to remove excess water, and allowed to drain Rinse 1litre of demineralised water, liquor to cloth ratio 25:1, 5 minute rinseRinse temperature 25° C. Spin cycle Each set of fabric swatches was spunindividually (to avoid cross contamination) in a spin dryer for 30seconds. Tumble dry Each set of fabric swatches was dried individuallyon normal setting

[0195] Evaluation

[0196] The Oxford cotton pieces were conditioned for 24 hours at 20° C.and 65% RH. The shear hysteresis (2HG5) of 6 fabric pieces was measuredin the centre of each piece in the warp direction. The average 2HG5 andthe standard deviation were calculated for each treatment. Treatmentscan only be compared within the experiment. Test 1 2 3 4 5 Clay of Clayof Clay of Clay of Clay of Example 1 Example 8 Example 4 Example 3Example 6 Additives 2HG5 2HG5 2HG5 2HG5 2HG5 Fabric 5.64 6.4 5.78 6.496.39 washing liquid formulation (A) Formulation 5.43 5.81 5.75 6.01 6.4(A) + additive 2.5% Formulation 5.16 5.89 5.76 6.16 5.9 (A) + additive5% Formulation 5.27 6.16 5.05 6.02 5.87 (A) + additive 10%

[0197] The results clearly demonstrate a reduction in 2HG5 whenadditives of the invention are included in the detergent composition.

EXAMPLE 20

[0198] Performance of functionalised clays in main wash and rinseapplication.

[0199] A simulated wash experiment was carried out. 200 ml local town'ssupply water heated to 40° C. Four (20×20 cm) unresinated cotton poplinsquares (20 g) added to the Linitest pot. Washing (with agitation)ensued for 30 minutes. Fabrics were subjected to two cold water rinsesfor 5 minutes each rinse. Fabrics were tumble dried, trimmed to 17×17 cmand conditioned for several hours in a humidity- controlled room.

[0200] The following detergent and fabric conditioning compositions wereused:

[0201] Formulation B: test wash detergent composition (granulardetergent) Weight % Na-LAS 10 Nonionics 7EO + 3EO 6 Zeolite A4 35 Sodaash 7

[0202] Formulation C: Fabric conditioning formulation: test conditioningformulation Weight % HEQ* 11 Coco 20EO 1 Tallow fatty acid 1 Minoringredients: perfume, stabilisers <5

[0203] The following tests were conducted:

[0204] 6. 1.0 g Formulation B+7% smectite clay (QPC 200 g) informulation applied in main wash

[0205] 7. 1.0 g Formulation B added along with 7% functionalised clay ofExample 1 in formulation.

[0206] 8. 1.0 g Formulation B added at start of wash. 0.5 mL formulationC applied in final rinse to give theoretical maximum active levels of0.3% on weight of fabric.

[0207] 9. 1.0 g Formulation B added at start of wash. 0.06 gfunctionalised clay of Example 1 added in final rinse

[0208] Experimental Summary Main Final rinse wash Ingredient Granulated(% max on Shear powder Additive (% in weight of hysteresis, Testcomposition formulation) fabric) 2HG5 6 Formulation QPC200G (7%) — 7.6(B) 7 Formulation Clay of — 7.1 (B) Example 1 (7%) 8 Formulation —Formulation 6.4 (B) (C) (0.3%) 9 Formulation — Clay of 6.0 B Example 1(0.3%)

[0209] Tests 6 and 7 compare the performance between unmodified smectiteclay against the clay of Example 1 in main wash. Tests 8 and 9 comparethe performance between a standard fabric conditioner and the clay ofExample 1 in the rinse at approximately equivalent active levels.

[0210] In each case the presence of the clay in accordance with theinvention provides a significant improvement.

EXAMPLE 21

[0211] Performance of Functionalised Clay Delivered from a FabricWashing Liquid Formulation

[0212] Washing Procedure

[0213] Wash Loads:

[0214] 20 Oxford pinpoint cotton 40×40 cm monitors (ex. TextileInnovators-TIC 410) and 20 poplin unresinated cotton 40×40 cm monitors(ex. Phoenix Calico) ballast used to make the load weight to 2.7 kg(100×100 cm woven cotton pieces)

[0215] Wash Conditions:

[0216] 32° C. wash (12 mins), 6° F.H ‘US’ water, 65 litres per wash (USWhirlpool machine)

[0217] 4 loads per treatment; fresh monitors and ballast used for eachwash.

[0218] each load tumble dried after every wash for 60 mins (US Whirlpoolelectric dryer, permanent press/heavy setting)

[0219] loads were removed immediately after the tumble dryer stopped

[0220] Treatments:

[0221] Formulation A of Example 19 (110 g)

[0222] Formulation A (100 g)+Clay of Example 1 (10 g)

[0223] Formulation A (100 g)+smectite clay (Gelwhite GP) (10 g)

[0224] Evaluation:

[0225] Wrinkle assessments were made after single washes for eachformulation on both poplin and Oxford cotton fabric constructions.

[0226] Monitors were panelled against an in-house wrinkle scale rangingfrom 0-10; where 0 is zero wrinkling and 10 is heavy wrinkling.

[0227] A selection of washed Oxford and poplin monitors were alsomeasured using Kawabata shear (a measure of lubrication).

[0228] Results Average Wrinkle scores Average (0-10 Kawabata wrinklescores scale) (2HG5) Oxford Poplin Oxford Poplin Formulation A 6.0 4.16.9 5.8 Formulation 5.9 3.9 6.6 5.7 A + Gelwhite clay Formulation 5.32.6 5.4 5.3 A + Clay of Example 1

[0229] Wrinkle Scores:

[0230] The difference between the results for Formulation A andFormulation A+functionalised clay of the invention when averaged overall single wash tests was approximately 0.7 units on the 0-10 scale onOxford cotton monitors and 1.5 scale units on poplin cotton monitors.Thus, these results clearly demonstrate a reduction in wrinkling when afunctionalised clay of the invention is included in the detergentcomposition.

[0231] Kawabata Scores:

[0232] Results from Kawabata measurements carried out on monitorsfollowing a single wash illustrate the increased level of lubricationdelivered to fabrics when a fuctionalised clay of the invention isincluded in the detergent composition.

1. Fabric treatment composition comprising a textile compatible carrierand particles having a layered structure comprising oxygen atoms andsilicon and/or phosphorus atoms, and comprising organic functionalgroups which are bonded to silicon and/or phosphorus atoms in the layersby direct covalent bonds between the silicon and/or phosphorus atoms anda carbon atom, characterised in that the functional groups are selectedfrom: (i) a group of the formula: —Y-T  (I) in which: Y comprises achain of at least 6 carbon atoms optionally interrupted by one or moreheteroatoms selected from N, O and S providing there are at least 3,preferably at least 4 carbon atoms for each heteroatom in the chain, Ybeing linked to said silicon or phosphorous atom through a carbon atom,and T represents H or a terminal group which is not capable ofself-cross-linking and/or forming covalent bonds to cellulosic and/orproteinaceous fibres during domestic washing and rinsing cycles; (ii) agroup of the formula: —R¹—NR²R² in which: R¹ represents an alkylenegroup of at least 4 carbon atoms, each R² is independently lower alkyland —NR²R² is preferably, but need not be, a terminal group; (iii) agroup of the formula: $\begin{matrix}\overset{+}{{—R}^{3}{—NR}^{4}R^{4}R^{4}} & ({III})\end{matrix}$

in which: R³ represents an alkylene group of at least 3 carbon atoms,each R⁴ is independently selected from alkyl groups of from 1 to 25carbon atoms provided at least one R⁴ is lower alkyl of 1 to 16 carbonatoms, (iv) a group of the formula

in which each R_(1a) group is independently selected from C₁₋₄ alkyl orhydroxyalkyl groups or C₂₋₄ alkenyl groups; each R_(2a) group isindependently selected from C₈₋₂₈ alkyl or alkenyl groups; R_(3a) is alinear or branched alkylene group of 1 to 5 carbon atoms, X is

and p is 0 or is an integer from 1 to 5, with the proviso that one ofR_(1a) and R_(2a) is an alkylene group of at least 3 carbon atomsattached to said silicon or phosphorus atom; (v) a group of the formula:

in which R_(1a), p and R_(2a) are as defined above; (vi) a group of theformula:

in which: T is as defined above, R⁵ represents a group of at least onecarbon atom, preferably at least 3 carbon atoms, which may beinterrupted by one or more heteroatoms selected from N, O and Sproviding there are at least 3 carbon atoms for each heteroatom, n is aninteger of at least 6; and (vii) a group of the formula:

in which: T and R⁵ are as defined above, each R⁶ independentlyrepresents an alkyl group, a fluorinated alkyl group, an aminosubstituted alkyl group, an alkyl group substituted with a sugar moiety,or a sidechain comprising an ethoxylated and/or propoxylated chain, andx is an integer of at least
 5. 2. A composition as claimed in claim 1 inwhich —Y-T is an alkyl group of from 6 to 20 carbon atoms.
 3. Acomposition as claimed in claim 1 in which each R2 is lower alkyl offrom 1 to 6 carbon atoms.
 4. A composition as claimed in claim 1 inwhich at least one of R2 is an alkyl group of at least 8 carbon atoms.5. A composition as claimed in claim 4 in which each R2 is an alkylgroup of at least 8 carbon atoms.
 6. A composition as claimed in claim 1in which T is selected from hydrogen, alkyl, ether, carboxylic acid, SO₃and SO₄ groups, phosphate and phosphonate.
 7. A composition as claimedin claim 1 in which the particles comprise two or more differentfunctional groups selected from formulas(I) to (VII).
 8. A compositionas claimed in claim 1 wherein the particles comprise layers whichfurther comprise atoms selected from magnesium, aluminiun, nickel,zirconium and mixtures thereof.
 9. A composition as claimed in claim 1wherein the particles are of a clay in which the organic functionalgroups have been introduced during formation of the clay.
 10. Acomposition as claimed in claim 1 wherein the particles are of anorganophyllosilicate.
 11. A composition as claimed in claim 1 which is amain wash detergent composition and wherein the textile compatiblecarrier comprises a detergent active compound.
 12. A composition asclaimed in claim 1 which is a fabric conditioner comprising one or morefabric softening or conditioning agents.
 13. A composition as claimed inclaim 1 comprising one or more further components selected from buildersand enzymes.
 14. A composition as claimed in claim 1 comprising from0.01% to 50% by weight of the particles.
 15. A composition as claimed inclaim 14 comprising from 0.1% to 20% by weight of the particles.
 16. Useof particles as defined claim 1 in the treatment of a fabric.
 17. Use ofparticles as defined in claim 1 to treat a fabric to provide enhancedlubricating properties to the fabric.
 18. Use of particles as defined inclaim 1 to treat a fabric to decrease the Kawabata shear of the fabricmeasured according to the Kawabata Shear Test defined herein.
 19. Use ofparticles as defined in claim 1 to treat a fabric to provide improvedsoftness and/or ease of ironing and/or anti-wrinkle properties and/oranti-abrasion properties.
 20. Use of a composition according to claim 1in the treatment of a fabric.
 21. Use of a composition according toclaim 1 to treat a fabric to provide enhanced lubricating properties tothe fabric.
 22. Use of a composition according to claim 1 to treat afabric to decrease the Kawabata shear of the fabric measured accordingto the Kawabata Shear Test defined herein.
 23. Use of a compositionaccording to claim 1 to treat a fabric to provide improved softnessand/or ease of ironing and/or anti-wrinkle properties and/oranti-abrasion properties.
 24. Use as claimed in any one of claims 16 to23 in which the treatment is part of a domestic laundering process. 25.A method of treating a fabric comprising contacting the fabric with afabric treatment composition as defined in claim
 1. 26. A compoundhaving a layered structure comprising oxygen atoms and silicon and/orphosphorus atoms, and comprising organic functional groups which arebonded to silicon and/or phosphorus atoms in the layers by directcovalent bonds between the silicon and/or phosphorus atoms and a carbonatom, characterised in that the functional groups are selected from: (i)a group of the formula: —R¹—NR²R²  (II) in which: R¹ represents analkylene group of at least 4 carbon atoms, each R² is independentlylower alkyl and —NR²R² is preferably, but need not be, a terminal group;(ii) a group of the formula: $\begin{matrix}\overset{+}{{—R}^{3}{—NR}^{4}R^{4}R^{4}} & ({III})\end{matrix}$

in which: R³ represents an alkylene group of at least 3 carbon atoms,each R⁴ is independently selected from alkyl groups of from 1 to 25carbon atoms provided at least one R⁴ is lower alkyl of 1 to 16 carbonatoms, (iii) a group of the formula

in which each RIa group is independently selected from C₁₋₄ alkyl orhydroxyalkyl groups or C₂₋₄ alkenyl groups; each R_(2a) group isindependently selected from C₈₋₂₈ alkyl or alkenyl groups; R_(3a) is alinear or branched alkylene group of 1 to 5 carbon atoms, X is

and p is 0 or is an integer from 1 to 5, with the proviso that one ofR_(1a) and R_(2a) is an alkylene group of at least 3 carbon atomsattached to said silicon or phosphorus atom; (iv) a group of theformula:

in which R_(1a), p and R_(2a) are as defined above; (v) a group of theformula:

in which: T represents H or a terminal groups which is not capable ofself-cross-linking and/or forming covalent bonds to cellulosic and/orproteinaceous fibres during domestic washing and rinsing cycles; R⁵represents a group of at least one carbon atom, preferably at least 3carbon atoms, which may be interrupted by one or more heteroatomsselected from N, O and S providing there are at least 3 carbon atoms foreach heteroatom, n is an integer of at least 6; and (vi) a group of theformula:

in which: T and R⁵ are as defined above, each R⁶ independentlyrepresents an alkyl group, a fluorinated alkyl group, an aminosubstituted alkyl group, an alkyl group substituted with a sugar moiety,or a sidechain comprising an ethoxylated and/or propoxylated chain, andx is an integer of at least
 5. 27. A compound as claimed in claim 26 inwhich each R² is lower alkyl of from 1 to 6 carbon atoms.
 28. A compoundas claimed in claim 26 in which at least one of R² is an alkyl group ofat least 8 carbon atoms.
 29. A compound as claimed in claim 26 in whicheach R² is an alkyl group of at least 8 carbon atoms.
 30. A compound asclaimed in claim 26 in which T is selected from hydrogen, alkyl, ether,carboxylic acid, SO₃ and SO₄ groups, phosphate and phosphonate.
 31. Acompound as claimed in claim 26 which comprises two or more functionalgroups selected from formulae (II) to (VII).
 32. A compound as claimedin claim 26 which additionally comprises a group of the formula:—Y-T  (I) in which Y comprises a chain of at least 6 carbon atomsoptionally interrupted by one or more heteroatoms selected from N, O andS providing there are at least 3, preferably at least 4 carbon atoms foreach heteroatom in the chain, Y being linked to said silicon orphosphorous atom through a carbon atom, and T represents H or a terminalgroup which is not capable of self-cross-linking and/or forming covalentbonds to cellulosic and/or proteinaceous fibres during domestic washingand rinsing cycles.